Lubricant



Patented June 27, 1950 UNITED STATES PATENT OFFICE 2,512,784

1 LUBRICANT a David a. Adelson, Berkeley, Calif., assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application December 26, 1946, Serial No. 718,617

This invention relates to new and novel reaction products having properties of greatly improving and stabilizing lubricants. This invention also pertains to lubricants, such as mineral lubricating oils, synthetic lubricants of hydrocarbon and non-hydrocarbon origin, and the like, containing therein a multi-functional additive having detergent and anti-ringsticking properties, as well as acting as an inhibitor of oxidation and corrosion.

. It is well known that various lubricants whether doped or undoped, tend to oxidize and to form corrosive bodies and sludge, when used in modern engines and machines operating under ordinary conditions or at high speeds, elevated temperatures, heavy loads and other adverse conditions. Some of the deterioration products of lu bricants formed during their use are hard carbonaceous materials which adhere to metal surfaces and cause scratching and scuffing of movable metal parts and the sticking of valves and .iston rings in engines. In addition, presently :Il'lOWn lubricants are generally incapable of maintaining a continuous lubricating film between movable metal parts, resulting in gradual or rapid wearing away of metal parts. The damage thus caused required replacement of such parts or even the complete overhauling of engines and machines, resulting in expensive loss of production and time.

In the case of the highest quality non-corrosive, stable lubricating oils, highly refined for specific use, or synthetic lubricants developed for specific or special uses, it has been observed that such oils and lubricants are generally highly susceptible to oxidation and deterioration, becoming progressively more corrosive in engines and machines even under ordinary operating conditions.

To improve the lubricating properties of oils and synthetic lubricants it has become the practice to blend with various lubricants, one and in most cases more than one addition agents, which have the efiect or property of inhibiting deterioration of lubricants and impart to them certain beneficial properties. Thus, additives have been specifically designed which have the property of inhibiting corrosion of alloyed bearings such as copper-lead, cadmium-silver and the like, developed for automotive, Diesel and aircraft engines. Acidic oxidation or decomposition components formed in lubricants during use readily attack these bearings but are inhibited or prevented from doing this by the formation of a corrosion protective film formed on the bearing surface with the aid of the additive.

12 Claims. (CL 252-482) also been developed whichpossess the property of modifying the carbonaceous materials formed, by deterioration of lubricants. on piston rods, rings and valves, and other metal parts in internal combustion engines, automotive and truck engines, aviation engines. high speed Diesel engines and the like. Such additives serve a very important function because, by modifying-this carbonaceous material so that it can be removed easily.v the tendency of engine parts to become stuck is inhibited so that ringsticking, piston scuiling, scratching and wearing away of other engine parts and material reduction of engine efficiency, are prevented or materially inhibited.

Other additives have been developed for the purpose of acting as detergents in lubricants in order to assist in the removal of soot or sludge, varnish, lacquer formed from deterioration of the oil when subjected to high operating temperatures. Detergents due to their cleaning action prevent the build up of these deleterious materials and assist in removing those formed. Antiwear additives have the property of reducing friction of movable metal parts of the same or different metals. Due to the function exerted or property imparted by such additives on lubricants, wear caused by direct frictional contact of metals can be greatly reduced. Also, additives have been developed o withstand extreme pressures, disperse impurities, solubilize certain additives and the like.

The development of numerous additives has been due to the fact that an additive is capable of functioning in only one specific manner. Very few lubricant additives have the ability of improving a. lubricant in more than just one respect. Thus, a good anti-oxidant might not be able to inhibit lacquer and varnish formation on piston rods or act as a detergent or corrosion inhibitor. In many cases it is found that an additive possesses very good properties in one respect, but is the cause of harmful formations and therefore detrimental as an additive in another respect.

Additives have To prevent this It is an object of this invention to improve the lubricating properties of various lubricating bases by the addition thereto of a minor amount of a multi-functional material. Another object of this invention is to add to compounded'or doped lubricants a multi-functional material whereby a synergistic effect is produced, resulting in a product of accentuated and improved properties. Another object of this invention is to add to oleaginous materials, mineral lubricating oils, synthetic lubricants and the like, a multi-functional material so as to inhibit oxidation and corrosion and prevent the formation of sludge, varnish and lacquer in said lubricants even under adverse operating conditions. Still another object of this invention is to use in lubricating compositions, a multi-functional material which prevents ringsticking as well as the sticking of other engine parts due to deterioration of the lubricant. Also it is an object of this invention to use in oleaginous materials, e. g. in lubricating compositions, a multi-functional material which inhibits wear, scuffing, scratching and other damage to engine parts. Furthermore it is an object of this invention to provide novel multi-functional improving and enhancing additives for lubricating bases. Other objects of this invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, this invention consists of features which will be hereinafter fully described, and particularly pointed out in the claims, the following description setting forth in detail certain embodiments of the invention, these being illustrative of but a few variations in which the principles of the invention may be employed.

Basically, this invention contemplates the use in lubricants reaction products obtained by reacting organic compounds with hydrogen sulfide in presence of ammonium hydrosulfide. Among the organic compounds which can be reacted with hydrogen sulfide in the presence of ammonium hydrosulfide to produce oil additives of this invention are:

I. ALIPHATIC HYDROCARBONS Acyclic compounds A. Saturated paraflinic hydrocarbons above 6 carbon atoms such as hexane heptane octane nonane tetradecane hexadecane eicosane tetracosane and the like. B. Unsaturated paraflinic hydrocarbons above 6 carbon atoms such as hexylene heptyiene polyolefines which may be broadly termed polyalkenes, and include polypropene, polypentenes as well as branched chain unsaturated hydrocarbons such as isc-olefines and iso-polyolefines.

Cyclic compounds A. Saturated cyclobutane cyclohexane cyclo-octane and the like.

B. Unsaturated cyclopentadiene cyclohexene cyclo-octene and the like.

II. AROMATIC HYDROCARBONS III. CYCLIC TERPENES cymene limonene pinene bornylene methene terpinolene terpin menthol menthone isoborneol camphor IV. HETEROCYCLIC COMPOUNDS furan, furfural, furiuryl alcohol, furoic acid, pyrone, pyridine, picolinic acid, nicotinic acid, pyran, morpholine, coumarone and the like.

Both the cyclic terpenes and the heterocyclic compounds can have attached thereto substituent radicals, such as alkyl and alkenyl radicals, hydrocy and halogen groups, and the like.

V. ALCOHOLS A. Aliphatic (saturated and unsaturated) amyl alcohol hexyl alcohol heptyl alcohol octyl alcohol decyl alcohol dodecyl alcohol octadecyl alcohol carnaubyl alcohol oleyl alcohol Polyhydric aliphatic alcohol glycols pinocols erythrol mannitol sorbitol and the like.

auavec .PHENOLlC COMPOUNDS Phenol. alkyl phenol, ,catechol, resorcinoi, p rogallol.

-,All of these'compounds may contain substituent groups such as. alkyl radicals, amino, halov gen, carbox'yl and the like, hydroquinone, quinone,"orcinol,phloroglucinol, cresols, thymol, saligenin, cinnamyl alcohol, methyl phenyl carbine],

eugenohcardanols, etc.

vn. ACIDS 1A., Aliphaticv (mono and polycarboxylic and h drox'y substituted acids and the like) capric undecyclic lauric myristic palmiticsteai'ic'- arachidic acids; acrylic: Q

\ sorbic, oleic, linoieic linolinic acids; Y -.hydroxy stearic" di and tri hydrocy stearic J ricinoleicacids;.

alkyl malonic acid alkyl succinic acid.

alkyl glutaric acid glycolic acid py oic'acid .phthalonic acid lactic acid alkyl maleic acid alkylmalic acid alkyl' tartaric acid.

1 alkyl citric acid -keto acids suberic acid -'alkyladipic acid 'tartronic acid i a v and the like, acids produced by oxidation of hydrocarbon e. g. g

- parafiin'wax and the like.

QB. Aromatic acids benzoic salicyclic 'cinnamic hydrocinnamic phthalic naphthoic abietic naphthenic and sulfonic -acids derived from petroleum hydrocarbons, mandelic acid, and the like; phenyl acetic acid phenyl stearic acid naphthyl stearic acid 'resinicacid" V v '0 Both the aromatic and aliphatic acids of group VII can have attached thereto substituent groups ,as'susgested under groups 11, III, and IV.

VIILESTERS Esters contemplatedicr use in this invention may be obtained by reactionins any of the compounds listed under groups V and VI and their derivatives, with any of the acids listed under group VII.

1x. ETHERS The ethers contemplated for use in this invention maybe symmetrical and unsymmetrical, or mixed ethers of dialkyl ethers, alkyl-aryl ethers,

arylethers and the like. Specifically it is des'irable to use:

Ether:

A. Aliphatic (saturated and unsaturated) methyl, ethyl methyl, ethyl, ethyl p pyl. i n opyl. octy ethers andthe like: vinyl, allyl, crotonyl ethers and the like and mixture oi satu-.

rated and unsaturated ethers. B. Cyclic, and poly ethers ethylene oxide propylene oxide aetal, dioxan and the like.

(3. Aromatic ethers anisole. phenetole, V

diphenyl, dixenyl,

dinaphthyl ethers,

benzyl'phenyl ether,

benzyl ether cardanoxyethanol "and the like.

. Substituted ethers l alkyloxy ethers of polyhydroxy aromatics $011 as resorcinal, pyrogallol, and the XALDEHYDES A. Aliphatic (saturated and unsaturated) acetaldehyde propionaldehyde 'butyraldehyde caproaldehyde and the like;

I acrolein, crotonaldehyde, citral, etc. 13. Aromatic Benzaldehyde l cinnamaldehyde salicylaldehyde naphthaldehyde vanil1in,etc.

Aliphatic (saturated and unsaturated) I 7 C. Cyclic ketones i Cyclobutanone cyclopentanone quinones cycloheptanone pure isophorone I -and isophorone bottoms the manufacture of which will be tuily describedhereinafter.

XII. NATURAL FATS, AND WARS AND THEIR DERIVATIVES AND MISCEL- LANEOUS COMPOUNDS A. Vegetable and animal oils, fats, and waxes such as: castor oil cocoanut oil corn oil cottonseed oil horse tat lard oil mutton tallow beef tallow neats-foot oil palm oil peanut oil rap seed oil soya bean oil 1 sperm oil whale oil wool tat Japan wax olefin waxes parailin waxes wax tailings petrolatum vegetable and animal phosphatidic materials montan wax 'carnauba wax v beeswax spermaceti I castor oil distillate ozokerite tall oil, and the like v B. Petroleum hydrocarbons such as:

- naphtha mineral seal oil kerosene gas oils, etc. mineral oil XIII. Metal salts and organic bases of organic.

acidic materials listed in any ofthe above groups, their mixtures, or various combinations may-be treated with hydrogen sulfide in presence of ammonium hydrosulfide. Metal bases include those .of the alkali metals, Cu,'Mg, Ca, Cr, Br, Zn, Cd,

Al, Sn, Pb, Cr, Mn, Fe, Ni, G0, etc. Organic bases include various nitrogen bases as primary, secondary, tertiary and quaternary amines.

Among the specific and preferred compounds contemplated for reacting with hydrogen sul-,

fide-in the'presence of ammonium hydrosulfide may be mentioned: stilbene, oleic acid, ammonium oleate, potassium oleate, ammonium undecylenate, ethyl undecylenate. methyl ricinoleate, cottonseed oil, rapeseed oil, peanut oil, dehydrated castor oil, and tall oil as well as wax oleflns, cinnamyl alcohol, pentanedione-2,4,diphenyl methane, high molecular weight saturated and unsaturated ketones, diacetone alcohol, mesityl oxide, ethyl oleate, ethyl cinnamate, cinnamaldehyde, and isophorone bottoms, the production and identification of which will befully described below.

Isopherone bottoms are primarily high molecular weight unsaturated ketones having at least 12 and preferably more than 18 carbon atoms in the molecule. The synthesis of these prod ucts is obtainedby condensation of acetone in caustic solution under elevated temperature and pressure. Specifically the product is obtained by condensing acetone in 30-60% caustic solution at a temperature ranging between about 130 -C. and about 170 C. and under pressure of from 300 to 500 pounds per square inch. The resultant product is subjected to distillation to remove distillable ketones and other constituents and impurities. The product remaining in the still is purified by filtration, solvent treatment and comprises of crude unsaturated cyclic ketones of high molecular weight, preferably referred to as crude isophoronebottoms. The term isophorone bottoms as referred herein is usually a complex mixture of high molecular weight unsaturated cyclic ketones containing at least 12 and preferably more than 18 carbon atoms in the molecule. The product thus tormedis not to be confused with straight isophorone which is specifically 3,5,5-trimethyl cyclohexene-2-onel, which is an unsaturated cyclic ketone containing only nine carbon atoms in the molecule.

Isophorone bottoms produced by condensation of acetone under conditions referred to above includes within its scope any and all unsaturated cyclic ketones containing at least 12 and 'preferably more than 18 carbon atoms and having generally the chemical structural configuration oi isophorone as' well as the chemical structural configuration resulting from its condensation.

Crudeisophorone bottoms can be fractionated and/01' chemically treated and each fraction therefrom can in turn be treated with phosphorus sulfide at elevated temperatures to produce a compound containing both phosphorus. and sulfur. Among the various fractions which can be obtained from crude isophorone bottoms are topped, crude isophorone bottoms which contain. at least 18 carbon atoms in the molecule and are obtainedafter removal of distillate from crude isophorone bottoms to a still head temperature of C. at 10 mm. mercury pressure. Another fraction of crude isophorone 'bottoms can be subjected to hydrolysis with dilute sodium hydroxide and the acetone and isophorone formed removed by distillation. Thebottoms can then be filtered and purified and comprise essentially unsaturated cyclic ketones containing at least 12 and moreca'rbon atoms in the molecule and are referred toas crude, hydrolyzed iso phorone bottoms. This material can be. subjected to distillation to split it into two fractions. The distilled hydrolyzed isophorone fraction has a boiling point of about 140 C. at 10 mm. mercury pressure and consists 01' a mixture of unsaturated cyclic ketones containing between 15 to 18 carbon atoms in 'the molecule. The residue is re- Crude isophorone botweight oi from 320 to 350. The heavier fraction or medium resin has a viscosity at 210' F. of about 80 to 120 centistokes and an average molecular weight of from 3'70 to 390. All of the various unsaturated cyclic ketone fractions obtained in the manner fully described above can be used for reacting with hydrogen'sulflde in the presence of ammonium hydrosulfide to form desired lubricating oil additives of this invention.

The reaction products of ammonium hydrosulfide-hydrogen sulfide with organic compounds can be prepared at room or elevated temperatures, preferably in enclosed vessels. No appar' ent advantage has been observed in using elevated temperatures to bring about the reaction except that it speeds up the reaction. However, the cost of fuel and special equipment outweighs this feature and it has been found more advantaseous to simply allow the ammonium hydrosulfide-hydrogen sulfide organic compound reactions to take place at room temperature in enclosed vessels for at least one week to one month or more depending upon the organic material being treated.

To more clearly illustrate the present invention, the following examples are presented. It is to be understood however that various modifications can be resorted to without departing from the spirit of the invention as presented in the subjoined claims.

EXANIPLE I isopropyl alcohol (700 cc.) contained in a 4- liter, thick-walled suction flask, was saturated with dry ammonia followed by dry hydrogen sulfide. A solution of 238.5 grams of topped, crude isophorone bottoms in 350 cc. isopropyl alcohol was added and the resulting solution was saturated with hydrogen sulfide. The side-neck and mouth of the flask were then closed and the flask was allowed to stand for a week with infrequent shaking. Upon opening the flask a partial vacuum was discovered. The reaction mixture was filtered to remove impurities and the isopropyl alcohol was removed from the filtrate by evaporation. The residue was dissolved in 500 cc. of a non-aromatic hydrocarbon having a boiling range of between about 164 F. and 233 F. and washed with water. After removal of the solvent in a current of nitrogen gas on a steam bath, a very viscous sticky mass was obtained, said mass possessing a pleasant odor and exhibiting much less flow at room temperature than did the starting materials. The product was oil-soluble and on analysis contained:

The same procedure was followed in this example as in Example I except that 243.5 grams of starting material was used and the reaction time was one month. The analysis of the resultant product was as follows:

Per cent by wt.- sulfur 8.3 (7) Per cent by wt. carbon 75.7 (8) Per cent by wt. hydrogen 9.6 (1) Per cent by wt. nitrogen 0.2 (7) Per cent by wt. oxygen r. 5.9 (7) Mol. wt 360 EXAMPLE III Per cent by wt. sulfur Per cent by wt. carbon 77.2 (3) Per cent by wt. hydrogen s 9.6 (2) Per cent by wt. nitrogen 0.3 (9) Per cent by wt. oxygen 6.5 (6) M01. wt 1 356 EXAMPLE IV Pure 3,5,5 trimethyl cyclohexene-2-one-1 was reacted with ammonium hydrosulfide-hydrogen sulfide as in Example I above and the analysis of the product was as follows:

Per cent by wt. sulfur 26.4 Per cent by wt. carbon 63.5 (5) Per cent by wt. hydrogen 8.9 (0) Per cent by wt. nitrogen 0.2 (5) Per cent by wt. oxygen 0.9 (0) EXAMPLE V Ethyl oleate (53.6 gm.) was treated with ammonium hydrosulfide and hydrogen sulfide in isopropyl alcohol solution for one week and the desired product removed as indicated in Example I. The product on analysis contained 4.0% sulfur and proved to be an excellent rust and wear inhibitor.

Attempts have been made to determine whether any improvement in the reaction product could be attained by removing the air from the reaction vessel and carrying out the reaction in a hydrogen sulfide atmosphere or by continuously replenishing hydrogen sulfide at regular intervals. Reaction products carried out under such condi: tions indicated that no advantage is obtained and it has therefore been preferred 'to carry out the reactions as indicated in the illustrative examples.

Other ammonium hydrosulfide-hydrogen sulfide-organic compound reaction products which are particularly preferable as lubricating 011 additives are as follows:

Ammonium hydrosulfide-hydrogen sulfide-mesityl oxide Ammonium hydrosulfide-hydrogen sulfide-diacetone alcohol Ammonium hydrosulfide-hydrogen sulfide-wax Ammonium hydrosulfide-hydrogen sulfide-stilbene Ammonium hydrosulfide-hydrogen sulfide-pentandione-2,4

.Ammonium hydrosulflde-hydrogen sulfide-diphenyl methane Ammonium hydrosulflde-hydrogen sulfide-oleic acid Ammonium hydrosulflde-hydrogen sulfide-ammonium oleate Ammonium hydrosulflde-hydrogen sulfide-potassium oleate Ammonium hydrosuliide-hydrogen sulfide-ammonium undecylenate Ammonium hydrosulfide-hydrogen sulfide-ethy undecylenate Ammonium hydrosulfide-hydrogen sulfide-ethyl cinnamate Ammonium hydrosulflde-hydrogen sulfide-methyl ricinoleate Ammonium hydrosulfide-hydrogen sulfide-cottonseed oil Ammonium hydrosulfide-hydrogen sulfide-rapeseed oil Ammonium hydrosulfide-hydrogen sulfide-peanut oil Ammonium hydrosulflde-hydrogen sulfide-dehydrated castor oil Ammonium hydrosulflde-hydrogen sulfide-tall oil Ammonium hydrosulfide-hydrogen sulfide-cinnamyl alcohol Ammonium hydrosulflde-hydrogen sulfide-cinnamaldehyde To illustrate the pronounced improvement obtained in lubricating compositions by the addition of small amounts of reaction products of this invention, the following test data are given:

TABLE I Oxidation stability determination A refined undoped lubricating oil, 64-67 S. U. at 210 F. was

employed, temperature 150 F.

X All oxidation products corrected to 1,800 mi. oxygen absorbed per 1%0 g.boi'd oil, assuming amount of product is proportioned to oxygen a 50: e

Additives of this invention were tested alone and compared with various lubricating oil additives in the multiple four-ball machine similar in principle to the Boerlage apparatus described in the magazine, Engineering, volume 136, July 14, 1933. This apparatus comprises four steel balls arranged in pyramid formation. The top ball is rotated by spindles against the three bottom balls which are clamped in a stationary ball holder.

'The balls are immersed in the oil to be tested.

Tests were run two hours at 700 R. P. ,M. under 7 Kg. load and at a controlled temperature of 130C. The diameters of the wear scars worn on the three balls forming the base of the pyramid were measured, and the average taken as the true indication of wear.

TABLE 11 Wear evaluation in the-multiple four-ball machine A refined undoped, lubricating oil, 6467 S. U. at 210' F. was employed.

The reaction products of this invention can be used as valuable constituents of heavy duty oils, motor oils, Diesel oils, aviation oils, turbine oil, synthetic oils and the like because of their anticorrosion, antioxidation, and antiwear properties. The amount of additive used can be varied over wide limits but generally it is not necessary to use more than 5% by weight of the reaction product and preferably only between about 0.1 to 2.0% by weight is added to base lubricants.

Because of its synergistic effect the reaction product of this invention can be combined with other additives in lubricants, such as, blooming agents, pour point depressants or viscosity improvers, extreme pressure agents, antifoaming agents and the like. Among the specific additives which can be used are oil-soluble detergents which include oil-soluble salts of various bases with detergent forming acids. Such bases include metal as well as organic bases. Metallic bases include those of the alkali metals, Cu, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases as primary, secondary, tertiary and quaternary amines.

Examples of detergent forming acids are the various fatty acids of, say, 10 to 30 carbon atoms, wool fat acids, paraflin wax acids (produced by oxidation of paraflin wax) chlorinated fatty acids, rosen acids, aromatic carboxylic acids including aromatic fatty acids, aromatic hydroxy fatty acids, paraffin wax benzoic acids, various alkyl salicylic acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acids, diphenols as di-(alkylphenol) sulfides and disulfides, methylene bis alkylphenols; sulfonic acids such as may be produced by treatment of alkyl aryl hydrocarbons or high boiling petroleum oils with sulfuric acid; sulfuric acid mono-esters; phosphoric.

arsonic and antimony acid mono and diesters,-

including the corresponding thio phosphoric, arsom'c and antimony acids; phosphonic and arsonic acids and the like.

Additional detergents are the alkaline earth phosphate diesters, including the thiophosphate diester; the alkaline earth diphenolatcs, speciilcally the calcium and barium salts of diphenol mono and poly sulfides.

Non-metallic detergents include compounds Antioxidants comprise several types, forextertiary-butyl phenol and the like; amino phenols as benzyl amino phenols; amines such as dibutylphenylene diamine, diphenyl amine, phenyl-beta-' naphthylamine, phenyl alpha naphthylamine, dinaphthyl amine.

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids; organic compounds containing an acidic 2. A lubricant comprising a major proportion of a mineral lubricatingoil and a minor amo t, but sufiicient to stabilize said mineral oil against deterioration and improve its anti-wear proper- .ties, of a stable, non-corrosive organic reaction product substantially free from nitrogen obtained by reacting for an extended period of time at between about roomtemperature and about 100 C. ammonium hydrosulfide-hydrogen sulfide with a ketone until from 4% to about 26.4% sulfur enters the reaction product.

3. A lubricant comprising a major proportion of a mineral lubricating oil and a minor amount,"

but sufflcient to stabilize said mineral oil against radical in close proximity to a nitrile, nitro or nitroso group (e. g. alpha cyano stearic acid).

Extreme pressure agents which may be used comprise: esters or phosphorous acidssuch as triaryl, alkyl hydroxy aryl, or aralkyl phosphates, thiophosphates or phosphites and the like; neutral aromatic sulfur compounds of relatively high boiling temperatures such as diaryl sulfides, diaryl disulfides, alkyl aryl disulfides, e. g. diphenyl sulfide, diphenol sulfide, dicresol sulfide, dixylenol sulfide, methyl butyl diphenol sulfide, dibenzyl sulfide, corresponding diand tri-sulfides, and the like; sulfurized fatty oils or esters of fatty acids and monohydric alcohols. e. g. sperm oil, jojoba oil, etc.; in which the sulfur is strongly bonded; sulfurized long chain olefins such as may be obtained by dihydrogenation or cracking of wax; sulfurized phosphorized fatty oils or acids, phosphorous acid esters having sulfurized organic radicals, such as esters of phosphoric or phosphorous acids with sulfurized hydroxy fatty acids; chlorinated hydrocarbons, such as chlorinated par-' affin, aromatic hydrocarbons, terpenes, mineral lubricating oil, etc. or chlorinated esters of fatty acids containing the chlorine in position other than alpha position.

Additional ingredients may comprise oil-soluble urea or thiourea derivatives, e. g. urethanes, allophanates, carbazides, carbazones, etc.; polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oil-soluble compounds.

Depending upon the additive use and conditions under which it is used, the amount of additive used may vary from 0.01 to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with phosphorous sulfide-unsaturated cyclic ketone reaction products of this invention.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however, is not to be limited thereto or otherwise restricted, except by the prior art and the scope of the appended claims.

I claim as my invention:

1. A lubricant comprising a major proportion of a mineral lubricating oil and a minor amount, but sufficient to stabilize said mineral oil against deterioration and improve its anti-wear properties, of a stable, non-corrosive organic reaction product substantially free from nitrogen obtained by reacting for an extended period of time and at between about room temperature and about 100 C. ammonium hydrosulfide-hydrogen sulfide with an oxygen-containing organic compound until from 4% to about 26.4% sulfur enters the reaction product.

deterioration and improve its anti-wear properties, or a stable, non-corrosive organic reaction product substantially free from nitrogen obtained by reacting for an extended period of time at between about room temperature and about C. ammonium hydrosulfide-hydrogen sulfide with an ester until from 4% to about 26.4% sulfur enters the reaction product.

4. A lubricant comprising a major proportionof a mineral lubricating oil and a minor amount, but sufficient to stabilize said mineral oil againstdeterioration and improve its anti-wear properties, of a stable, non-corrosive organic reaction product substantially free from nitrogen obtained by reacting, at between about room temperature andabout 100 C. ammonium hydrosulfide-hydrogen sulfide with a salt of an organic acid until from 4% to about 26.4% sulfur enters the reaction product.

5. A lubricant comprising a major proportion of a mineral lubricating oil and a minor amount,

but suficient to stabilize said mineral oil againstdeterioration and improve its anti-wear properties, of a stable, non-corrosive organic reactionproduct substantially free fromhitrogen obtained by reacting, at between about room temperature and about 100 0., ammonium hydrosulfide-hydrogen sulfide with an unsaturated cyclic ketone fraction having at least 12 or more carbon atoms and derived from condensation of acetone to isophorone type fractions of high molecular weight until from 4% to about 26.4% sulfur enters the reaction product.

6. A lubricant comprising a major proportion of a mineral lubricating oil and a minor amount, but sufficient to stabilize said mineral oil against deterioration and improve its anti-wear properties, of a stable, non-corrosive organic reaction product substantially free from nitrogen obtained by reacting, for an extended period of time and at between about room temperature and about 100 C. ammonium hydrosulfide, hydrogen sulfide with ethyl oleate until from 4% to about 26.4% sulfur enters the reaction product.

7. A-lubrlcant comprising a major proportion of a mineral lubricating oil and a minor amount,

but sufficient to stabilize said mineral oil against detergents, and a small amount of an oil additive reaction product substantially free from nitrogen obtained by treating an oxygen-containing organic compound with ammonium hydrosulfidehydrogen sulfide at between about room temperature and about 100' C. for a period ranging from between about 5 hours to over one month until from 4% to about 26.4% sulfur enters the reaction product.

9. A lubricant comprising a major proportion of a mineral lubricating oil and a minor amount, but suificient to stabilisesaid mineral oil against deterioration and improve its anti-wear properties, of a stable, non-corrosive organic reaction product substantially free from nitrogen obtained by reacting, at between about room temperature and about 100' 0., ammonium hydrosulfide-bydrogen sulfide with an unsaturated cyclic ketone fraction, having at least 12 carbon atoms until said reaction product contains at least 0.2% sulfur and up to about 28.4% sulfur.

10. A lubricant comprising a major proportion of a mineral lubricating oil and a minor amount, but suifieient to stabilise said mineral oil against deterioration and improve its anti-wear properties. of a stable, non-corrosive organic reaction product substantially free from nitrogen obtained by reacting, at between about room temperature and about 100' C., ammonium hydrosulfide-hydrogen sulfide with ethyl oieate until said reaction product contains atleast 4.0% sulfur and up to about 28.4% sulfur.

11. A lubricant comprising a major proportion of a mineral lubricating oil and a minor amount. but suilicient to stabilize said mineral oil against deterioration and improve its anti-wear properties, of a stable, non-corrosive organic reaction product substantially free from nitrogen obtained 16 by reacting, at between about room temperature and about100 0., ammonium hydrosulfide-hydrogen sulfide with an oxygen-containing organic compound until said reaction product contains at least 4.0% sulfur and up to about 26.4% sulfur. 12. A lubricant comprising a major proportion of a mineral lubricating oil and a minor amount, but sufiicient to stabilize said mineral oil against deterioration and improve its anti-wear properties of a stable non-corrosive organic reaction product substantially free from nitrogen obtained by reacting at between about room temperature and about 100 C., ammonium hydrosulflde-hydrogen sulfide with isophorone bottoms comprising essentially unsaturated cyclic ketone fractions having at least 18 carbon atoms in the molecule. until said reaction product contains at least 0.2% sulfur and up to about 26.4% sulfur.

DAVID E. ADELSON.

REFERENCES CITED The following references are of record in th file of this patent:

UNITED STATES PATENTS Number Name Date 2,230,691 Lewis Feb. 4, 1941 2,279,560 Dietrich Apr. 14, 1942 2,413,849 Ott Dec. 31, 1946 2,489,249 Adelson Nov. 29, 1949 

1. A LUBRICANT COMPRISING A MAJOR PROPORTION OF A MINERAL LUBRICATING OILA ND A MINOR AMOUNT, BUT SUFFICIENT TO STABILIZE SAID MINERAL OIL AGAINST DETERIORATION AND IMPROVE ITS ANTI-WEAR PROPERTIES, OF A STABLE, NON-CORROSIVE ORGANIC REACTION PRODUCT SUBSTANTIALLY FREE FROM NITROGEN OBTAINED BY REACTING FOR AN EXTENDED PERIOD OF TIME AND AT BETWEEN ABOUT ROOM TEMPERATURE AND ABOUT 100*C. AMMONIUM HYDROSULFIDE-HYDROGEN SULFIDE WITH AN OXYGEN-CONTAINING ORGANIC COMPOUND UNTIL FROM 4% TO ABOUT 26.4% SULFUR ENTERS THE REACTION PRODUCT. 